DE60225539T2 - METHOD FOR CONTINUOUS PRODUCTION OF POLYARYLENEULFIDE - Google Patents

Description

TECHNICAL FIELD

The The present invention relates to a process for the preparation of Polyarylene sulfide. More specifically, it relates to a method for continuous production of polyarylene sulfide, which is a high Has molecular weight and has excellent thermal stability.

BACKGROUND OF THE INVENTION

polyarylene (which will be abbreviated to "PAS" in the following), in particular polyphenylene sulfide (which in the following partially abbreviated to "PPS"), is known as a special plastic, which has excellent properties in terms of mechanical strength and heat resistance and so on and what good electrical properties and has high rigidity. Therefore, it becomes prevalent in used a variety of materials, such as electronic Components, electrical components and mechanical components. Especially becomes a molded article with a resin composition comprising a polyphenylene sulfide and an inorganic filler for one Used variety of uses.

In a conventional one Conventional method of producing a PAS becomes a dihalogenated aromatic compound, such as p-dichlorobenzene, with an alkali metal sulfide, such as sodium sulfide and lithium sulfide, in an aprotic organic polar solvent, such as N-methyl-2-pyrrolidone (NMP) mixed and a prescribed Amount of water added to the process as the alkali metal sulfide in a polar solvent insoluble is. Under these circumstances For example, the alkali metal sulfide is dissolved in a polar solvent in the presence of Dissolved water and a part thereof becomes an alkali metal hydrosulfide by hydrolysis transformed. The thus formed alkali metal hydrosulfide prevented however, improvements in the molecular weight of the PAS and converts an end group of the polymer into an -SH group and leads in this way the process to a PAS with lower thermal stability.

In order to solve the problems described above, there has been proposed in the patent literature a method of producing a high molecular weight PAS in which water is added to the raw materials and then preliminary polymerization is carried out at a low temperature [see published US patent no Japanese Patent Application No. 9228/1989 (Show 64)], a method comprising conducting a preliminary polymerization in which a small amount of water is added to the raw materials to increase the conversion of the alkali metal sulfide and then the polycondensation is carried out by adding water to the raw materials Japanese Patent Application No. 7332/1986 (Shows 61)] and similar.

however All of the above methods are common and always separate not yet satisfactory for producing a PAS, which is a high Having molecular weight and excellent thermal stability, suitable.

DESCRIPTION OF THE INVENTION

The The present invention has been made in view of the above problems made. An object of the present invention is to provide a method for the continuous production of a PAS, which has a high molecular weight and excellent thermal stability. Another object of the present invention is to provide a PAS, which has a high molecular weight and excellent thermal stability and further comprising a composition containing the PAS.

in the With regard to the above-described problems has been mentioned by the Inventors an intense and detailed Research and development program launched and carried out. When a result from this was found now that in the case of a Process for producing a PAS by reacting a dihalogenated aromatic compound with a sulfur source such as a metal sulfide in a polar solvent the tasks of present invention can be achieved by the polymerization reaction carried out with the addition of a certain excess of the dihalogenated aromatic Connection in proportion to the sulfur source and to maintain the content of the dihalogenated aromatic compound in the polymerization medium after completion the polymerization reaction at or above a certain excess.

Consequently the objects of the present invention have been solved on Based on the above results and information. Especially The core and spirit of the present invention lies in one continuous process for producing a polyarylene sulfide, which is the reaction of a sulfur starting material with a dihalogenated aromatic compound in an aprotic organic solvent characterized in that the content of the dihalogenated aromatic compound in the polymerization liquid after the material Completion of the polymerization reaction in the range of 5 to 20 mg / g is maintained.

BEST MODE FOR CARRYING OUT THE INVENTION

in the The following will be a more detailed one Presentation of the present invention presented.

1. Manufacturing method for a PAS

The Process for the continuous production of a polyarylene sulfide according to the present The invention includes the reaction of a sulfur precursor with a dihalogenated one aromatic compound in an aprotic organic solvent and is characterized by the maintenance of the content of dihalogenated aromatic compound in the polymerization liquid after the material completion of the polymerization reaction in the Range from 5 to 20 mg / g.

(1) Compounds as starting materials

-1- Dihalogenated aromatic compound

The dihalogenated aromatic compound used in the preparation process according to the present invention is used, for example, dihalogenated benzene such as Example p-dihalogenated benzene and m-dihalogenated benzene, alkyl-substituted dihalogenated benzene, cycloalkyl substituted dihalogenated Benzene and so forth such as 2,3-dihalogenated toluene; 2,5-dihalogenated Toluene; 2,6-dihalogenated toluene; 3,4-dihalogenated toluene; 2,5-dihalogenated xylene; 1-ethyl-2,5-dihalogenated benzene; 1,2,4,5-tetramethyl-3,6-dihalogenated Benzene; 1-n-hexyl-2,5-dihalogenated Benzene; and 1-cyclohexyl-2,5-dihalogenated benzene, aryl substituted dihalogenated benzene such as 1-phenyl-2,5-dihalogenated benzene; 1-benzyl-2,5-dihalogenated benzene; and 1-p-toluyl-2,5-dihalogenated benzene, Dihalobiphenyls such as 4,4'-dihalobiphenyl, dihalonaphthalenes such as for example, 1,4-dihalonaphthalene; 1,6-Dihalonaphthalen; and 2, 6-dihalonaphthalenes, and similar, however, p-dichlorobenzene is particularly preferred.

-2- Agrotic organic solvent

Examples of preferred aprotic organic solvents to be used generally include organic polar solvents, such as Amide compounds, lactam compounds, urea compounds, organosulfur compounds and cyclic organophosphorus compounds, each alone as a single solvent or in a mixture as solvent mixture can be used.

The above-mentioned amide compounds in the group of polar solvents are for example. N, N-dimethylformamide; N, N-diethylformamide; N, N-dimethylacetamide; N, N-diethylacetamide; N, N-dipropylacetamide; N, N-dimethylbenzoic acid amide, etc.

The The above-mentioned lactam compounds are, for example, caprolactam and N-alkyl-caprolactams such as N-methylcaprolactam; N-ethylcaprolactam; N-Isopropylcaprolactam; N-Isobutylcaprolactam; N-n-Propylcaprolactam; N-n-butylcaprolactam; and N-cyclohexylcaprolactam; N-methyl-2-pyrrolidone (NMP); N-ethyl-2-pyrrolidone; N-isopropyl-2-pyrrolidone; N-isobutyl-2-pyrrolidone; N-n-propyl-2-pyrrolidone; N-n-butyl-2-pyrrolidone; N-cyclohexyl-2-pyrrolidone; N-methyl-3-methyl-2-pyrrolidone; N-ethyl-3-methyl-2-pyrrolidone; N-methyl-3,4,5-trimethyl-2-pyrrolidone; N-methyl-2-piperidone; N-ethyl-2-piperidone; N-isopropyl-2-piperidone; N-methyl-6-methyl-2-piperidone; N-methyl-3-ethyl-2-piperidone, etc.

The The above-mentioned urea compounds are, for example, tetramethylurea; N, N'-dimethylethyleneurea; N, N'-dimethylpropylene, etc.

The The above-mentioned organosulfur compounds are, for example, dimethylsulfoxide; diethyl; diphenyl sulfone; 1-methyl-1-oxosulfolane; 1-ethyl-1-oxosulfolane; 1-phenyl-1-oxosulfolane; etc.

The The above-mentioned organophosphorus compounds are, for example, 1-methyl-1-oxophospholane; 1-n-propyl-1-oxophospholan; 1-phenyl-1-oxophospholan, etc.

each the example mentioned above Aprotic organic polar solvents can be used alone used or as a mixture with at least one other mentioned or also in a mixture with a solvent which is not included in the list above, but with the proviso that the purpose and the solution of the present invention is not affected by the mixing.

From the various aprotic organic exemplified above polar solvents are N-alkylcaprolactams and N-alkylpyrrolidones preferred, very particularly preferred is N-methyl-2-pyrrolidone.

-3- sulfur starting materials

Mainly find as a sulfur source metal sulfides use, typically a Alkali metal compound such as sodium sulfide, lithium sulfide and potassium sulfide. Each of the above sulfur sources can hereby used alone or in combination with at least another of the above, or an alkaline earth metal sulfide, or a sulfur source other than those mentioned above.

-4- phase separation agent

It It is preferred that as the phase separation agent lithium chloride, sodium acetate and a salt of an alkali metal such as lithium, water and so on, with lithium chloride being most preferred is used.

-5- Others

According to the present The invention may include a comonomer, a branching reagent, an end group reagent and so on in combination with the above dihalogenated aromatic compound can be used. The comonomer can be used for Example 2,3-dichlorophenol; 2,3-dibromophenol; 2,4-dichlorophenol; 2,4-dibromophenol; 2,5-dichlorophenol; 2,5-dibromophenol; 2,4-dichloroaniline; 2,4-dibromoaniline; 2,5-dichloroaniline; 2,5-dibromoaniline; 3,3-dichloro-4,4'-diaminobiphenyl; 3,3-dibromo-4,4'-diaminobiphenyl; 3,3-dichloro-4,4'-dihydroxybiphenyl, 3,3-dibromo-4,4'-dihydroxybiphenyl; Di (3-chloro-4-amino) phenylmethane; m-dichlorobenzene; m-dibromobenzene; o-dichlorobenzene; o-dibromobenzene; 4,4'-dichlorodiphenyl ether; and 4,4'-dichlorodiphenylsulfone include.

The Branching reagent may be, for example, 1,2,4-trichlorobenzene; 1,3,5-trichlorobenzene; 1,2,3-trichlorobenzene; 2,5-dichloronitrobenzene; and 2,4-dichloronitrobenzene include.

The End group reagent may be chlorobenzene; bromobenzene; iodobenzene; p-chloronitrobenzene; o-chloronitrobenzene; p-chlorocyanobenzene; o-chlorocyanobenzene; and halogenated phenol such as p-bromophenol; m-bromophenol; o-bromophenol; p-chlorophenol; m-chlorophenol; o-chlorophenol; p-fluorophenol; m-fluorophenol; o-fluorophenol; p-iodophenol; m-Todphenol; and o-iodophenol. Of these, p-bromophenol and p-chlorophenol preferred.

(2) Preparation of PAS

-1- amount of used as starting material serving raw material

The A process for producing a polyarylene sulfide according to the present invention Invention is characterized in that the content of the dihalogenated aromatic compound in the polymerization liquid after the material Completion of the polymerization reaction in the range of 5 to 20 mg / g is maintained, preferably in the range of 6 to 20 mg / g. This approach makes it possible, in an efficient way to obtain a PAS which has a high molecular weight and has excellent thermal stability. Under the expression "after the material Completion of the Polymerization Reaction "as used herein the time understood to be the polymerization process End, that is, the timing at the output of a continuous operated polymerization reactor.

In the case of the continuous production of a PAS according to the present invention, by using a sulfur source with a dihalogenated aromatic compound as essential starting materials is reacted, the amount of raw materials to be used can be determined so as to maintain the content of the dihalogenated aromatic compound in the polymerization liquid after the completion of the polymerization reaction in the above-mentioned range.

More accurate said, amounts the amount of dihalogenated aromatic compound to be used preferably at least 1.05 based on the molar ratio to Sulfur source, more preferably in the range of 1.06 to 1.20 based on the said molar ratio. One of the mentioned Range deviating molar ratio sometimes leads to the impossibility to guarantee a PAS which has a high molecular weight and has excellent thermal stability.

in the In case of using water, the amount to be used is preferably in the range of 0.05 to 4.0 based on the molar ratio to Sulfur source, more preferably in the range of 0.1 to 3.0 to the said molar ratio. A molar ratio below 0.05 includes the risk an insufficient one Whereas a molar ratio above 4.0 Risk of impossibility involves producing a high molecular weight PAS.

Around the polymerization reaction according to the present To accelerate the invention may include a metal hydroxide such as an alkali metal compound and / or N-methylaminobutyric acid salt a metal such as N-methylaminobutyric acid salt an alkali metal to the reaction system in addition to the above Starting materials are added. The amount of to be added Additive is preferably in the range of 0.01 to 1.0 based the molar ratio to the metal sulfide, more preferably in the range of 0.05 to 0.8 based on the said molar ratio.

-2- reaction conditions

The above-mentioned polymerization reaction within the production process according to the present invention may be at a temperature in the range of 230 to 290 ° C, preferably 240 to 280 ° C, more preferably 250 to 270 ° C carried out become. Before the polycondensation, a preliminary polymerization in a Temperature in the range of 180 to 230 ° C, preferably 190 to 220 ° C, especially preferably 195 to 215 ° C are performed. The reaction time of the polycondensation is in the range of 0.5 to 10 hours, preferably 1.0 to 10 hours, more preferably 1.5 to 10 hours. When the reaction time is less than 0.5 hours is, there is a risk of insufficient Reaction and thus gives only an insufficient increase in molecular weight the PAS, wherein when the reaction time is more than 10 hours, the renewal not as effective as expected.

in the The scope of the present invention is the number of polymerization stages in the polymerization kettle is not particularly limited and it can multi-stage process and the temperature conditions are applied can changed per level become.

Also are in the context of the method according to the present invention usable polymerization kettle and the stirrer are not particularly limited, however it is preferred that the polymerization kettle corresponds to a type, good for a complete Mixing is suitable and the stirrer is preferably a large-sized stirrer such as a Vollzonenrührer.

The after completion of the main polymerization polymerization solution obtained be subjected to a washing step by adding so much water is that the PAS will not get stuck. The amount of water, which with the amount and temperature of the polymerization solution varies, should not exceed a lot, which leads to a solidification or precipitation PAS leads due to excessive cooling. It This is generally advantageous, the contents of the wash tank to stir so that the polymerization solution and the water is sufficiently mixed together.

The usable washing solutions are not particularly limited however allowed the adhering to the polymer impurities or by-products not through the solution lead to adverse effects on the polymer in the wash medium. Possible washing solutions are for example, methanol, acetone, benzene, toluene, water and NMP, however Water is preferred.

To At the completion of the polymerization reaction, the polymerization solution is dissolved in fed to a separation vessel in which the solution is subjected to a separation step will be the solution in a polymer phase and a solvent phase to separate.

Around to increase the efficiency of the washing and separation step the washing and separation steps advantageously used repeatedly.

According to the present invention, it is further preferred to remove the solvent since the polymer phase still contains solvents after completion of the washing and separation steps. Here, the separation step for the solvent is not particularly limited and can be carried out according to an already known solvent removal method in a production process for PAS, such as a so-called "Abflash" method as disclosed in, for example Japanese Patent Application No. 33878/1995 (Heisei 7).

To At the end of the solvent removal process, the PAS may be in a molten state are taken from the process or but after cooling with a suitable cooling method also in the form of granules. Here, the cooling method, for example, with cooling Air, with water, with oil or similar be.

2. Polyarylene sulfide (PAS)

The PAS, which according to the method of the present invention has a sufficient Molecular weight, inclusive an inherent viscosity [η] of at least 0.10, preferably at least 0.14, and a melt index [MI] from 0 to 1000 g / 10 minutes. Such a resin, as just described, which has excellent thermal stability properties is for various purposes can be used under harsh conditions.

The above-mentioned inherent viscosity was measured with an Ubbelohde viscometer for a 0.4 g / deciliter solution of according to the preceding described polyarylene sulfide in alpha-chloronaphthalene at 206 ° C certainly.

When another method of analysis for the thermal stability can according to the present Invention advantageously be used a method which the Observation of changes the inherent viscosity [η] of the PAS using blends of PAS with NMP and annealing the mixture at high temperature (265 ° C) for 8 hours. In this Method is the mixing ratio of PAS to NMP arbitrarily, however, the reproducibility of the results to improve, the analysis is usually carried out, by equivalents Quantities (masses) of the two individual components are mixed, for Example in each case 2.5 g. Furthermore, it is under consideration the solubilities the corresponding resins conveniently the inherent viscosity [η] at 206 ° C indicate.

wobei R¹ ein Substituent darstellt ausgewählt aus einer Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einer Alkoxygruppe, einer Phenylgruppe, einem Metallsalz einer Carbonsäure, einer Aminogruppe, einer Nitrogruppe oder einem Halogenatom wie zum Beispiel Fluor, Chlor oder Brom; m ist eine ganze Zahl von 0 bis 4; und n ist ein mittlerer Polymerisationsgrad im Bereich von 10 bis 200:

wobei n wie bereits definiert ist.The PAS obtained according to the production method according to the present invention is a polymer containing at least 70 mol% of the repeating unit, which can be expressed, for example, by the structural formula Ar-S-wherein Ar represents an aryl group. Typical PAS according to this formula are PPS containing at least 70 mol% of the repeating unit according to the structural formula (I) and a PPS containing at least 70 mol% of the repeating unit according to the structural formula (II):

wherein R ^{1 represents} a substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, a metal salt of a carboxylic acid, an amino group, a nitro group or a halogen atom such as fluorine, chlorine or bromine; m is an integer of 0 to 4; and n is a mean degree of polymerization in the range of 10 to 200:

where n is as already defined.

The Process for the preparation of PAS according to the present invention is suitable for the production of PAS with any known Structure including a substantially linear molecular structure without branches or networked structures and a molecular structure with branches or networked structures, said structures depending on Manufacturing process can be produced. For example, that can PAS be a homopolymer or copolymer which serves as a repeat unit at least 70 mol%, preferably at least 80 mol%, of a para-phenylene sulfide unit contains. Examples of the structural units for the copolymerization include meta-phenylene sulfide, ortho-phenylene sulfide units, p, p'-diphenylene ketone sulfide units, p, p'-diphenylene sulfone sulfide units, p, p'-Biphenylensulfideinheiten, p, p'-Diphenylenethersulfideinheiten, p, p'-Diphenylenmethylensulfideinheiten, p, p'-Diphenylencumenylsulfideinheiten and naphthenesulfide units.

A Another object of the present invention is the provision a polyarylene sulfide resin which is not only dissolved by the described polyarylene sulfides, but also by the Providing a polyarylene sulfide having a substantially linear Structure, a branched or crosslinked polyarylene sulfide, in which is a small amount of a monomer which is at least three having functional groups together with the other monomers is polymerized and a polymer blend from the just described Polyarylene sulfide with the above-described polyarylene sulfide with essentially linear structure.

The PAS resin composition according to the present invention Invention contains 20 to 90 wt.%, Preferably 20 to 70 wt.%, Particularly preferably 40 to 70 wt.% Of PAS, which according to the manufacturing method described above and 80 to 10 wt.%, Preferably 80 to 30 wt.%, particularly preferably 60 to 30% by weight of an inorganic filler. Examples of the inorganic filler include glass fibers, carbon fibers, aramid fibers, potassium titanate whiskers (Needle-shaped Single crystals), silicon carbide whiskers, mica ceramic fibers, wollastonite, Mica, talc, silicon, aluminum, kaolin, clay, silicon - aluminum, Carbon black, calcium carbonate, Titanium oxide, lithium carbonate, molybdenum disulfide, graphite, iron oxide, Glass beads, calcium phosphate, calcium sulfate, magnesium carbonate, magnesium phosphate, Silicon nitride and hydrotalcite. Any of the above fillers can each for used or in combination with at least one other become. From the above fillers Glass fibers are particularly preferred.

in this connection The fiber is not particularly limited and may vary depending on the purpose selected are made of alkali glass, low alkali glass and alkali-free Glass. The length the fibers is preferably 0.1 to 8 mm, particularly preferably 0.3 to 6 mm, and the Diameter of the fibers is preferably 0.1 to 30 microns (microns), especially preferably 0.5 to 25 microns. is the length fibers less than 0.1 mm this to lower reinforcement effects, whereas lengths above 8 mm lead to a decrease in the flowability of the mixture. One Diameter of the fibers below 0.1 microns leads to a decrease in flowability the resin, whereas diameter of the fibers from above 30 microns to lesser Strength the mix leads. The configuration of the fiber is not particularly limited and can be chosen from a variety of forms such as Roving, ground fibers and cut strands. The glass fiber can here used alone or in blends with other fillers.

Around the compatibility To improve the glass fiber with the resin, the glass fiber can be one surface treatment be subjected to a silane-based coupling agent Aminosilane-based, epoxysilane-based, vinylsilane-based or methacrylic-silane-based a titanate-based coupling agent based on tetramethyl orthotitanate or tetraethyl orthotitanate base, a chromium complex or a Boron compound.

Farther is the process for preparing the composition of the PAS resin according to the present Invention not particularly limited. The composition can for example, by blending the PAS, an inorganic one filler and an additive as required, such as a silane-based coupling agent, an antioxidant, a heat stabilizer, a Lubricant, a plasticizer, a conductivity blocker, a colorant and pigment; Mix the components together using a Tumbler, Henschelmischers or similar; and the entry of resulting mixture in a melt kneader to a melt granules using a single-screw extruder or multi-screw extruder or using a kneader, Banbury mixer or the like to obtain.

One Molded part according to the present For example, the invention can be made from the PAS composition described above are produced by injection molding or extrusion melting or a similar one Method.

By the process for the continuous production of a polyarylene sulfide according to the present invention characterized by the maintenance of the content of the dihalogenated aromatic compound in the polymerization liquid after the material Completion of the polymerization reaction in the range of 5 to 20 mg / g it is possible a high molecular weight polyarylene sulfide and simultaneously excellent thermal stability properties.

The from the method according to the present invention Invention available PAS can be used advantageously as a material for a large variety of molded parts such as for example as material for Films, fibers, mechanical components, electrical components, electronic Components and so on.

In In the following, the present invention will be described in even greater detail with reference to examples. Investigations were also performed in terms of the concentration of PDCB, the inherent viscosity of the PAS and its thermal stability using the following rules:

{Measurement of concentration of PDCB}

The Concentration of PDCB was using a method using an internal standard with the help of a gas chromatograph Use of chloroform as the diluting solvent and 1,2,4-TCB as internal standard.

{Thermal stability determination method}

A miniaturized pressure-tight cell, which has an internal volume of 10 milliliters (mL) and made of SUS stainless steel 316 was prepared with 2.5 g PAS and 2.5 g N-methyl-2-pyrrolidone (NMP) loaded and hermetically sealed. The cell was then in an oil bath heated to raise the temperature to 265 ° C and there for 8 hours held. Thereafter, the cell was removed from the oil bath and cooled, and then the PAS was removed from the cell, washed with water and dried. Then, the inherent viscosity [η] of the dried PAS according to the following Measured method.

{Measurement of inherent viscosity}

A sample of the PAS weighing 0.04 +/- 0.001 g was dissolved in 10 mL of alpha-chloronaphthalene at 235 ° C over 15 minutes, and viscosity measurements of the resulting solution were made in a thermostated at 206 ° C thermostat and the Viscosity of pure alpha-chloronaphthalene free of the PAS polymer determined to determine the relative viscosity. The inherent viscosity [η] was determined according to the following formula using the relative viscosity thus obtained. [η] (deciliter / g) = In (relative viscosity) / concentration of the polymer

example 1

preliminary polymerization

A 1 m ³ kettle for the synthesis of titanium starting materials equipped with a stirrer was charged with 633 kg of N-methyl-2-pyrrolidone (NMP) and 100 kg (2.38 kilomole) of lithium hydroxide (LiOH.H ₂ O). charged and the resulting mixture was heated to 140 ° C and held at this temperature. The water contained in the starting lithium hydroxide was removed by batchwise distillation. Subsequently, 65 N-kiloliters of gaseous hydrogen sulfide were blown into the mixture maintained at a temperature of 130 ° C to produce lithium hydrosulfide.

Subsequently was stopped the supply of hydrogen sulfide and the synthesis boiler heated again to a temperature of 205 ° C. Together with the warming The reaction mixture is also the by-product of the reaction removed with hydrogen sulfide water by batchwise distillation, while was formed from the lithium hydrosulfide lithium sulfide.

Upon completion of the reaction, the reaction product contained 1.08 kilomole of lithium sulfide and 0.214 kilomole of lithium N-methyl-4-aminobutyrate. Under the condition of a temperature of 205 ° C, 168.3 kg (1,145 kilomoles) of p-dichlorobenzene (PDCB) and further 5.3 kg of pure water were added to the reaction product, and the reaction was continued at 210 ° C for 3 hours. Then, the reaction solution became 60 ° C or lower cooled and the resulting reaction mixture was transferred from the kettle to a 20 liter kettle. Sales to PDCB was 85%.

Continuous polymerization

One 10 liters autoclave, equipped with a Vollzonenrührer was charged with 855 g of lithium chloride as a phase release agent and 5145 g of NMP and heated to a temperature of 260 ° C. The above made prepolymer was at 60 ° C stored and continuously to the reactor with an inflow rate of 33.3 g / minute metered using a gear pump.

On the other side was about 150 to 200 g of the polymerization mixture from the reactor a drain valve approximately deducted every 5 minutes for a constant level maintain the reactor. The procedure was for 24 hours continued and the samples taken by means of a decantation filter technique separated into the polymer and the polymerization. Then it became measured the concentration of PDCB in the polymerization liquor. The resulting polymer was washed twice with hot water and further with acetone washed and then dried in vacuo at 120 ° C for 12 hours the inherent viscosity [η] and Δ [η]. The results are shown in Table 1.

Example 2

The Method according to Example 1 was repeated to turn a PAS To obtain polymerization mixture with the deviation that the Amount of p-dichlorobenzene (PDCB) used of 168.3 kg (1,145 kilomoles) changed to 171.4 kg (1.166 kilomoles) has been. The results of the tests carried out analogously to Example 1 are also shown in Table 1.

Example 3

The Method according to Example 1 was repeated to turn a PAS To obtain polymerization mixture with the deviation that the Amount of p-dichlorobenzene (PDCB) used of 168.3 kg (1,145 kilomoles) changed to 174.6 kg (1.188 kmol) has been. The results of the tests carried out analogously to Example 1 are also shown in Table 1.

Comparative Example 1

The procedure of Example 1 was repeated to again obtain a PAS polymerization mixture except that the amount of p-dichlorobenzene (PDCB) employed was changed from 168.3 kg (1.145 kilomole) to 162.0 kg (1.102 kilomole). The results of the tests carried out analogously to Example 1 are likewise reproduced in Table 1. TABLE 1 Concentration PDCB (mg / g) [η] (dl / g) Δ [η] (dl / g) example 1 6.5 0.31 0.03 Example 2 9.5 0.26 0.02 Example 3 11.9 0.24 0 Comparative Example 1 4.1 0.26 0.18

INDUSTRIAL APPLICABILITY

polyarylene is known as a plastic material that is exceptional in its mechanical strength is and its heat resistance and so on and the good electrical properties and has a has high rigidity. As such, it becomes widespread for a variety used in materials such as electronic components, electrical components and mechanical components. In particular, a moldings of a resin composition of polyphenylene sulfide and an inorganic one Filler for a variety used by various applications.

Claims (9)

A process for continuous production a polyarylene sulfide which comprises reacting a sulfur precursor with a dihalogenated aromatic compound in an aprotic organic solvents, characterized by maintaining the content of the dihalogenated aromatic compound in the polymerization liquid after the material Completion of the polymerization reaction in the range of 5 to 20 mg / g. The production method according to claim 1, wherein the content the dihalogenated aromatic compound in the polymerization liquid after the material completion of the polymerization reaction in the range from 6 to 20 mg / g is maintained. The production process according to claim 1, wherein the dihalogenated aromatic compound in a ratio of at least 1.05, expressed based on the molar ratio the dihalogenated aromatic compound / sulfur source in the polymerization reaction. The production process according to claim 1, wherein the dihalogenated aromatic compound in a ratio of 1.06 to 1.20 in terms of terms on the molar ratio the dihalogenated aromatic compound / sulfur source in the polymerization reaction. The production process according to claim 1, wherein the polymerization reaction in the presence of a phase demixing agent. The production process according to claim 1, wherein the polymerization reaction carried out in the presence of water becomes. The production process according to claim 1, wherein the polyarylene sulfide a logarithmic viscosity number (η) of has at least 0.1. A polyarylene sulfide resin composition which comprises from 20 to 90% by weight of the polyarylene sulfide obtained after the in one of the claims 1 to 7 is produced and 80 to 10 Weight% of an inorganic filler. A molded article formed by molding the produced in claim 8 polyarylene sulfide resin composition is.